WO2020235498A1 - 樹脂組成物及び成形品 - Google Patents

樹脂組成物及び成形品 Download PDF

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WO2020235498A1
WO2020235498A1 PCT/JP2020/019497 JP2020019497W WO2020235498A1 WO 2020235498 A1 WO2020235498 A1 WO 2020235498A1 JP 2020019497 W JP2020019497 W JP 2020019497W WO 2020235498 A1 WO2020235498 A1 WO 2020235498A1
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Prior art keywords
resin composition
component
composition according
resin
polyphenylene ether
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PCT/JP2020/019497
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English (en)
French (fr)
Japanese (ja)
Inventor
美希 徳山
希 稲垣
美穂子 山本
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旭化成株式会社
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Priority to CN202080032500.7A priority Critical patent/CN113767144A/zh
Priority to EP20810735.9A priority patent/EP3971239B1/en
Priority to US17/595,449 priority patent/US20220251375A1/en
Priority to JP2021520770A priority patent/JP7656534B2/ja
Publication of WO2020235498A1 publication Critical patent/WO2020235498A1/ja

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
    • C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
    • C08L71/12—Polyphenylene oxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C08L23/12—Polypropene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/346—Clay
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/14—Glass
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
    • C08L53/025—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes modified
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C08K2003/267—Magnesium carbonate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/005—Additives being defined by their particle size in general
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/08—Polymer mixtures characterised by other features containing additives to improve the compatibility between two polymers

Definitions

  • the present invention relates to a resin composition and a molded product.
  • Polypropylene resin is excellent in molding processability, water resistance, oil resistance, acid resistance, alkali resistance, etc., but has the drawback of being inferior in heat resistance, rigidity, and impact resistance. Therefore, a polyphenylene ether resin is blended with this polypropylene resin so that the polypropylene resin forms a matrix and the polyphenylene ether resin forms dispersed particles, thereby producing a resin composition having improved heat resistance and rigidity. Is being done.
  • Patent Document 1 describes that solvent resistance and impact resistance are improved by blending polyphenylene ether with polyolefin
  • Patent Documents 2 and 3 describe polyphenylene ether. Is described as improving impact resistance by blending with polyolefin and hydrogenated block copolymers.
  • Patent Documents 4 to 9 a specific hydrogenated block copolymer is blended with a resin composition composed of a polyolefin resin and a polyphenylene ether resin to obtain a resin composition having excellent chemical resistance and processability. Is described.
  • the alloy material of polypropylene and polyphenylene ether resin is used for automobile parts and water parts. Since water-related parts are expected to be used at water pressure and high temperature, heat resistance, water resistance, impact resistance, rigidity, and vibration fatigue characteristics are required, and an inorganic filler reinforcing material is required.
  • the alloy material of polypropylene and polyphenylene ether resin has excellent water resistance, it has been found that the interface between the inorganic filler and the resin is weak against water and acid, and the physical properties deteriorate when immersed in water and acid. ..
  • the conventional polypropylene / polyphenylene ether resin compositions as proposed in Patent Documents 1 to 9 have a problem in terms of water resistance when glass fibers are added.
  • an object of the present invention is to provide a polypropylene / polyphenylene ether resin composition having excellent water resistance even when an inorganic filler is added.
  • the present inventors have added a hydrotalcite-like compound to the polypropylene / polyphenylene ether composition to alleviate the deterioration of physical properties in water when the inorganic filler is added.
  • the present invention has been reached by finding that excellent water resistance can be obtained even when an inorganic filler is added, which has not been achieved in the past.
  • a resin composition containing (a) a polyphenylene ether-based resin, (b) a polypropylene-based resin, (c) an admixture, (d) an inorganic filler, and (e) a hydrotalcite-like compound.
  • F The resin composition according to [1], further comprising a polyolefin modified with an unsaturated carboxylic acid.
  • the resin composition according to [1] or [2], wherein the Charpy impact strength without a notch is 10 kJ / m 2 or more.
  • the admixture (c) is one selected from the group consisting of a hydrogenated block copolymer, a copolymer having a polystyrene block chain-polyolefin block chain, and a copolymer having a polyphenylene ether block chain-polyolefin block chain.
  • a polypropylene / polyphenylene ether resin composition having excellent water resistance can be obtained even when an inorganic filler is added.
  • a phase containing a linear (c) admixture having a length of 75 nm or more in 10 or more of the phases containing the component (a) is a phase containing the component (a). It is an image observed by TEM that it is dispersed in a state of being contained inside.
  • the phase containing the linear (c) admixture having a length of 75 nm or more in 10 or more of the phases containing the component (a) is the phase containing the component (a). It is an image observed by TEM that it is dispersed in a state of being contained inside.
  • the phase containing the linear (c) admixture having a length of 75 nm or more in 10 or more of the phases containing the component (a) is the phase containing the component (a). It is an image observed by TEM that it is dispersed in a state where it is not contained inside.
  • a phase containing a linear (c) admixture having a length of 75 nm or more in 10 or more of the phases containing the component (a) is a phase containing the component (a). It is an image observed by TEM that it is dispersed in a state where it is not contained inside.
  • the present embodiment a mode for carrying out the present invention (hereinafter, referred to as “the present embodiment”) will be described in detail.
  • the present invention is not limited to the following embodiments, and can be variously modified and implemented within the scope of the gist thereof.
  • the resin composition of the present embodiment is a composition containing (a) a polyphenylene ether-based resin, (b) polypropylene, (c) an admixture, (d) glass fiber, and (e) a hydrotalcite-like compound.
  • the resin composition of the present embodiment can obtain a polypropylene / polyphenylene ether resin composition having excellent water resistance even when an inorganic filler is added, and further, the water resistance of the molded product, Heat resistance, impact resistance, rigidity, and vibration fatigue characteristics can be arranged side by side.
  • (A) Polyphenylene ether-based resin Specific examples of the (a) polyphenylene ether-based resin in the present embodiment include poly (2,6-dimethyl-1,4-phenylene ether) and poly (2-methyl-6-ethyl-1,4). -Phenylene ether), poly (2-methyl-6-phenyl-1,4-phenylene ether), poly (2,6-dichloro-1,4-phenylene ether) and the like, and further 2,6-dimethylphenol. And a polymer with other phenols (for example, a polymer with 2,3,6-trimethylphenol or 2-methyl-6-butylphenol as described in Japanese Patent Publication No. 52-17880).
  • Polyphenylene ether copolymers such as copolymers
  • polyphenylene ethers include poly (2,6-dimethyl-1,4-phenylene ether), a copolymer of 2,6-dimethylphenol and 2,3,6-trimethylphenol, or these. It is a mixture.
  • the method for producing the component (a) is not particularly limited as long as it can be obtained by a known method, and for example, U.S. Pat. Nos. 3,306,874, 3,356,875, and 325,357. Examples thereof include the production methods described in the specification of No. 3257358, Japanese Patent Application Laid-Open No. 50-51197, Japanese Patent Application Laid-Open No. 52-17880, and Japanese Patent Application Laid-Open No. 63-152628.
  • the lower limit of the preferable range of the reduced viscosity of the component (a) in the present embodiment is 0.30 dL / g, more preferably 0. It is .032 dL / g, more preferably 0.035 dL / g.
  • the upper limit of the preferable range of the reduced viscosity is 0.80 dL / g, more preferably 0.75 dL / g, and further preferably 0.55 dL / g.
  • component (a) of the present embodiment even a blend of two or more kinds of polyphenylene ethers having different reducing viscosities can be used.
  • stabilizers for stabilizing polyphenylene ether, various known stabilizers can be preferably used.
  • stabilizers are metal-based stabilizers such as zinc oxide and zinc sulfide, hindered phenol-based stabilizers, phosphorus-based stabilizers, and organic stabilizers such as hindered amine-based stabilizers.
  • A Less than 5 parts by mass with respect to 100 parts by mass of the component.
  • a known additive or the like that can be added to the polyphenylene ether may be added in an amount of less than 10 parts by mass with respect to 100 parts by mass of the component (a).
  • the polypropylene-based resin is not particularly limited, and examples thereof include homopolymers and / or copolymers having propylene as a repeating unit structure, and examples thereof include crystalline propylene homopolymers and crystalline propylene-.
  • a mixture of an ethylene block copolymer, a crystalline propylene homopolymer and a crystalline propylene-ethylene block copolymer is preferable.
  • the crystalline propylene-ethylene block copolymer is not particularly limited, and examples thereof include those having a crystalline propylene homopolymer portion and a propylene-ethylene random copolymer portion.
  • the melt mass flow rate (hereinafter, also referred to as “MFR”) of the component (b) is 0.1 g from the viewpoint of suppressing drawdown during combustion and enhancing the balance between fluidity and mechanical strength of the resin composition. It is preferably / 10 minutes or more, more preferably 0.3 g / 10 minutes or more, particularly preferably 0.5 g / 10 minutes or more, and preferably 15 g / 10 minutes or less. , 6 g / 10 minutes or less is more preferable, and 3 g / 10 minutes or less is particularly preferable.
  • the MFR conforms to ISO1133 and can be measured under the conditions of a temperature of 230 ° C. and a load of 2.16 kg. Specifically, MFR can be measured by the method described in Examples described later.
  • the method for producing the component (b) is not particularly limited, and a known method can be used.
  • Specific examples of the method for producing polypropylene include a temperature of 0 to 0 to 0 in the presence of a polymerization catalyst composition containing an alkylaluminum compound and a titanium halide catalyst supported on a carrier such as a titanium trichloride catalyst or magnesium chloride. Examples thereof include a method of polymerizing propylene under the conditions of 100 ° C. and a pressure of 3 to 100 atm.
  • a chain transfer agent such as hydrogen may be added in order to adjust the molecular weight of the polymer.
  • an electron-donating compound is used as an internal donor component or an external donor component in the polymerization system. Further can be included.
  • the electron donating compound include ester compounds such as ⁇ -caprolactone, methyl methacrylate, ethyl benzoate, and methyl tolulate; phosphite esters such as triphenyl phosphite and tributyl phosphite; hexa.
  • Phosphoric acid derivatives such as methylphosphoric triamide; alkoxy ester compounds; aromatic monocarboxylic acid esters; aromatic alkylalkoxysilanes; aliphatic hydrocarbon alkoxysilanes; various ether compounds; various alcohols; various phenols and the like. ..
  • the polymerization method in the above method may be either a batch method or a continuous method, and the polymerization method includes solution polymerization or slurry polymerization using a solvent such as butane, pentane, hexane, heptane, or octane, and further, no polymerization method.
  • the solvent may be used as a bulk polymerization method in a monomer, a gas phase polymerization method in a gaseous polymer, or the like.
  • the method for producing the crystalline propylene-ethylene block copolymer is not particularly limited, and for example, the first step of obtaining the crystalline propylene homopolymer portion.
  • the other ⁇ -olefin is not particularly limited, and examples thereof include propylene, 1-butene, 1-hexene and the like.
  • the total content of the component (a) and the component (b) is 100% by mass when the resin composition of the present embodiment is 100% by mass, from the viewpoint of impact resistance and production stability of the resin composition. , 30% by mass or more, preferably 35% by mass or more, further preferably 40% by mass or more, and 80% by mass or less, preferably 75% by mass or less, preferably 70% by mass. It is more preferably% or less.
  • the preferable content ratio of the component (a) and the component (b) is that the content of the component (a) is 100 parts by mass when the total amount of the component (a) and the component (b) is 100 parts by mass. It is 10 to 70 parts by mass, and the content of the component (b) is 30 to 90 parts by mass. More preferably, the content of the component (a) is 10 to 60 parts by mass, the content of the component (b) is 40 to 90 parts by mass, and even more preferably, the content of the component (a) is 10 to 60 parts by mass.
  • the content of the component (b) is in the range of 50 to 90 parts by mass.
  • the content ratio of the component (a) and the component (b) is in this range, the balance between impact resistance, heat resistance and tensile strength is excellent, which is preferable.
  • These ratios in the resin composition can be determined by the calibration curve method using Fourier transform infrared spectroscopy (FT-IR).
  • the resin composition of the present embodiment can form a matrix phase containing the component (b) and a dispersed phase containing the component (a). Thereby, the heat-resistant creep property of the obtained resin composition can be further improved.
  • the component (c) is preferably a copolymer having a segment block chain having a high compatibility with the component (a) and a segment block chain having a high compatibility with the component (b).
  • High compatibility means that the phase is not separated.
  • segment block chain having high compatibility with the component (a) examples include polystyrene block chain and polyphenylene ether block chain.
  • segment block chain having high compatibility with the component (b) examples include a polyolefin block chain and a copolymer elastomer block chain of ethylene and ⁇ -olefin.
  • component (c) shall not be included in the range of the component (a) and the component (b).
  • the component (c) is selected from the group consisting of, for example, a hydrogenated block copolymer, a polystyrene block chain-polyolefin block chain copolymer, and a polyphenylene ether block chain-polyolefin block chain copolymer. More than seeds can be mentioned. Among these, hydrogenated block copolymers are preferable from the viewpoint of further excellent thermal stability.
  • the component (c) may be used alone or in combination of two or more.
  • the hydrogenated block copolymer at least a part of the block copolymer containing a polymer block a mainly composed of a vinyl aromatic compound and a polymer block b mainly composed of a conjugated diene compound is hydrogenated.
  • the hydrogenated block copolymers obtained include the hydrogenated block copolymers obtained.
  • the polymer block a mainly composed of a vinyl aromatic compound and the total amount of 1,2-vinyl bond and 3,4-vinyl bond are 30 to 90%. It is preferably a hydrogenated block copolymer containing a polymer block b mainly composed of a certain conjugated diene compound.
  • the total amount of 1,2-vinyl bond and 3,4-vinyl bond of the conjugated diene compound in the polymer block b is 30 to 90% from the viewpoint of compatibility with the polyphenylene ether resin and vibration fatigue characteristics. Is preferable.
  • the polymer block a is preferably a homopolymer block of a vinyl aromatic compound or a copolymer block of a vinyl aromatic compound and a conjugated diene compound.
  • "mainly composed of a vinyl aromatic compound” means that the polymer block a contains a vinyl aromatic compound unit in an amount of more than 50% by mass. From the viewpoint of further excellent molding fluidity, impact resistance, weld and appearance, it is preferable that the polymer block a contains 70% by mass or more of vinyl aromatic compound units.
  • Examples of the vinyl aromatic compound constituting the polymer block a include styrene, ⁇ -methylstyrene, vinyltoluene, p-tert-butylstyrene, diphenylethylene and the like. Of these, styrene is preferable. These may be used alone or in combination of two or more.
  • the number average molecular weight of the polymer block a is not particularly limited, but is preferably 15,000 or more. Further, it is preferably 50,000 or less. By setting the number average molecular weight of the polymer block a within the above range, the impact resistance of the resin composition of the present embodiment can be further improved.
  • the number average molecular weight of the polymer block a can be measured by GPC (mobile phase: chloroform, standard substance: polystyrene).
  • the polymer block b is preferably a homopolymer block of a conjugated diene compound or a random copolymer block of a conjugated diene compound and a vinyl aromatic compound.
  • "mainly a conjugated diene compound” means that the polymer block b contains a conjugated diene compound unit in an amount of more than 50% by mass. From the viewpoint of further excellent molding fluidity, impact resistance, weld and appearance, it is preferable that the polymer block b contains 70% by mass or more of the conjugated diene compound unit.
  • Examples of the conjugated diene compound constituting the polymer block b include butadiene, isoprene, 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene and the like. Of these, butadiene, isoprene and combinations thereof are preferable. These may be used alone or in combination of two or more.
  • the amount of 1,2-vinyl bond and 3,4-vinyl with respect to the total amount of vinyl bond contained in the conjugated diene compound constituting the polymer block is preferably 30 to 90%, more preferably 45 to 90%, and 65 to 90%. Is more preferable.
  • the total vinyl bond amount of butadiene in the polymer block b is preferably 65 to 90%.
  • the total vinyl bond amount can be measured by an infrared spectrophotometer. The calculation method is described in Analytical Chemistry, Volume 21, No. 8. It can be carried out according to the method described in August 1949.
  • the component (c) is preferably a hydrogenated block copolymer of a block copolymer containing at least a polymer block a and a polymer block b.
  • the components in (c) include, for example, ab, ab-a, and b-ab. Examples thereof include hydrogenated vinyl aromatic compound-conjugated diene compound block copolymers having structures such as -a, (ab-) 4Si, and a-b-ab-a.
  • Si in (ab-) 4Si is a reaction residue of a polyfunctional coupling agent such as silicon tetrachloride or tin tetrachloride, or a residue of an initiator such as a polyfunctional organolithium compound.
  • a polyfunctional coupling agent such as silicon tetrachloride or tin tetrachloride
  • an initiator such as a polyfunctional organolithium compound.
  • the molecular structure of the block copolymer containing the polymer block a and the polymer block b is not particularly limited, and may be, for example, linear, branched, radial, or any combination thereof. ..
  • the distribution of the vinyl aromatic compound or the conjugated diene compound in the molecular chain in each polymer block is random or tapered (monomer component increases or decreases along the molecular chain). It may be in the form of a partial block, or any combination thereof.
  • the two or more polymer blocks may have the same structure or different structures. Good.
  • the hydrogenated block copolymer of the component (c) is derived from the vinyl aromatic compound contained in the block copolymer before hydrogenation from the viewpoint of further excellent molding fluidity, impact resistance, weld and appearance.
  • the unit is preferably 20 to 95% by mass.
  • the lower limit of the content of the structural unit may be 30% by mass or more, 40% by mass or more, 50% by mass or more, 60% by mass or more, and the upper limit may be 85% by mass or less, 75% by mass or less, 65% by mass or more. Hereinafter, it may be 55% by mass or less.
  • the content of the structural unit derived from the vinyl aromatic compound can be measured by an ultraviolet spectrophotometer.
  • the number average molecular weight (Mn) of the block copolymer before hydrogenation is preferably 5,000 to 1,000,000.
  • the lower limit of the number average molecular weight (Mn) may be 10,000 or more, 20,000 or more, 40,000 or more, 60,000 or more, and the upper limit may be 800,000 or less, 500,000 or less, 200, It may be 000 or less, 100,000 or less, or 80,000 or less.
  • the number average molecular weight (Mn) can be measured by gel permeation chromatography (GPC, mobile phase: chloroform, standard substance: polystyrene).
  • the molecular weight distribution of the block copolymer before hydrogenation is preferably 10 or less.
  • the molecular weight distribution can be calculated by obtaining the ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) measured by GPC (GPC, mobile phase: chloroform, standard substance: polystyrene). ..
  • the hydrogenation rate of the double bond derived from the conjugated diene compound in the component (c) is not particularly limited, but is preferably 50% or more, preferably 80% or more, from the viewpoint of further excellent heat resistance. More preferably, it is more preferably 90% or more.
  • the hydrogenation rate can be measured by NMR.
  • the method for producing the hydrogenated block copolymer of the component (c) is not particularly limited, and a known production method may be adopted.
  • the above-mentioned hydrogenated block copolymer was grafted or added with ⁇ , ⁇ -unsaturated carboxylic acid or a derivative thereof (ester compound or acid anhydride compound). , It may be a modified hydrogenated block copolymer.
  • the modified hydrogenated block copolymer is the above-mentioned hydrogenated block copolymer and ⁇ , in the presence or absence of a radical generator in the molten state, the solution state or the slurry state in the range of 80 to 350 ° C. It is obtained by reacting with ⁇ -unsaturated carboxylic acid or a derivative thereof. In this case, it is preferable that ⁇ , ⁇ -unsaturated carboxylic acid or a derivative thereof is grafted or added to the hydrogenated block copolymer at a ratio of 0.01 to 10% by mass. Further, it may be a mixture of the above-mentioned hydrogenated block copolymer and the modified hydrogenated block copolymer in an arbitrary ratio.
  • the content of the component (c) in the present embodiment is, when the resin composition of the present embodiment is 100% by mass, 2% by mass or more and 5% by mass from the viewpoint of impact resistance of the resin composition. It is preferably 7% by mass or more, more preferably 30% by mass or less, preferably 25% by mass or less, and further preferably 15% by mass or less.
  • (D) Inorganic filler As the surface-treated inorganic filler (d) used in the present embodiment (hereinafter, also simply referred to as the component (d)), known ones can be used without particular limitation, and a fibrous filler can be used. , Plate-like filler is preferable.
  • the fibrous filler examples include, but are not limited to, glass fibers, carbon fibers, whiskers such as potassium titanate whiskers, calcium silicate (wallastonite), and the like.
  • the plate-shaped filler is not limited to these, and examples thereof include glass flakes, mica, and talc.
  • glass fiber is most preferable from the viewpoint of rigidity and water resistance. These may be used individually by 1 type, and may be used in combination of 2 or more type.
  • the surface treatment for the inorganic filler is not particularly limited, and examples thereof include surface treatment using various coupling agents such as silane type and titanate type.
  • the surface treatment using a silane coupling agent such as aminosilane or epoxysilane. Is preferable.
  • Judgment as to whether or not the glass fiber contains an acid functional group can be made based on whether or not an acid-derived peak is detected when the surface treatment agent for the glass fiber is extracted in chloroform and measured by Py-GC / MS. it can.
  • Examples of the acid constituting the compound containing an acid functional group include unsaturated carboxylic acids or derivatives thereof such as maleic acid, fumaric acid, itaconic acid, acrylic acid, tetrahydrophthalic acid, citraconic acid, crotonic acid and isocrotonic acid.
  • Saturated carboxylic acid and the like can be mentioned, and examples of the derivative thereof include anhydride, acid halide, amide, imide, ester and the like.
  • Specific examples thereof include maleic anhydride, acetic anhydride, succinic anhydride, monomethyl maleate, dimethyl maleate, maleimide, and glycidyl maleate.
  • silane-based coupling agent (silane coupling agent) used for the surface treatment is not particularly limited, but is preferably 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, N-2- (aminoethyl). -3-Aminopropylmethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane.
  • the inorganic filler As a method of surface treatment for the inorganic filler, for example, when the inorganic filler is glass fiber, when the fibrous inorganic filler is spun and converged, a silane coupling agent is applied to the surface together with a sizing agent, and then dried. There is a way to make it.
  • the inorganic filler is in the form of short fibers or powder, a method of impregnating the silane coupling agent solution with these fillers and then drying the filler can be mentioned.
  • the temperature at the time of drying is preferably 100 ° C. or higher.
  • the inorganic filler When the inorganic filler is fibrous and is a filler, it has a fiber length of 2 mm or more when it is delivered from the inorganic filler manufacturer (before kneading with an extruder).
  • the inorganic filler is fibrous and is a filler
  • the one having an average fiber diameter of 20 ⁇ m or less is preferable from the viewpoint of water resistance
  • the one having an average fiber diameter of 5 to 15 ⁇ m is preferable from the viewpoint of the balance of mechanical properties and dimensional characteristics, and is 12 to 14 ⁇ m. Is the most preferable.
  • the average fiber diameter refers to the average fiber diameter per fibrous filler measured by observing the fibrous filler with a scanning electron microscope (SEM), and is an average of any 10 fibers. Good.
  • the ratio (R / H) of the average plate diameter (R) to the average thickness (H) of the plate is 5 or more from the viewpoint of sufficiently obtaining the reinforcing effect of the filler. It is preferably 10 or more, more preferably 20 or more, and particularly preferably 20 or more.
  • the content of the above-mentioned component (d) when the resin composition of the present embodiment is 100% by mass, the melt fluidity of the resin composition, vibration fatigue characteristics, heat resistance, surface appearance of the molded product, and the molded product From the viewpoint of the specific gravity of the above, it is preferably 5% by mass or more, preferably 7% by mass or more, further preferably 10% by mass or more, and less than 50% by mass and 40% by mass or less. Is preferable, and it is more preferably 35% by mass or less.
  • hydrotalcite-like compound examples include hydrotalcites described in JP-A-60-2141 and JP-A-9-59475, for example, hydrotalcite compounds represented by the following formulas. Can be used. [M 2+ 1-x M 3+ x (OH) 2 ] x + [An - x / n ⁇ mH 2 O] x- (.A shown wherein, M 2+ is Mg 2+, Mn 2+, Fe 2+ , a divalent metal ion of Co 2+, etc., M 3+ is Al 3+, Fe 3+, trivalent metal ions of C 3+ like n- is CO 3 2-, OH -, HPO 4 2-, .x indicating the anion SO 4 2-like n-valent (particularly monovalent or divalent) is 0 ⁇ x ⁇ 0.5, m is , 0 ⁇ m ⁇ 1.)
  • the hydrotalcite-like compound may be natural or synthetic.
  • the hydrotalcite-like compound may be calcined hydrotalcite in which the amount of OH in the chemical structure is reduced by calcining. Further, the hydrotalcite-like compound may be surface-treated.
  • the hydrotalcite-like compound is available from Kyowa Chemical Industry Co., Ltd. as "DHT-4A”, “DHT-4A-2”, “Alchemizer”, "KW-2200” and the like.
  • the hydrotalcite-like compound is preferably uniformly dispersed in the resin, and the average particle size of the hydrotalcite-like compound is preferably 1 nm or more and 2 ⁇ m or less from the viewpoint of impact resistance, and is 1 nm or more and 1.5 ⁇ m or less. It is more preferably 1 nm or more and 1.0 ⁇ m or less.
  • the average particle size refers to the average particle size per particle of the hydrotalcite-like compound measured by observing the molded piece using a scanning electron microscope (SEM), and is measured for each particle.
  • SEM scanning electron microscope
  • the average of the major axis and the minor axis may be the average value for any 10 particles.
  • the content of the component (e) in the present embodiment is 0.01% by mass or more from the viewpoint of water resistance and vibration fatigue characteristics of the resin composition when the resin composition of the present embodiment is 100% by mass. Yes, it is preferably 0.03% by mass or more, more preferably 0.05% by mass or more, and more preferably 20% by mass or less, preferably 15% by mass or less, and 5% by mass or less. Is more preferable.
  • polyolefin resin (the ⁇ , ⁇ -unsaturated carboxylic acid or a derivative thereof is 0.01 to A 10% by weight graft or addition) polyolefin resin may be used, and a mixture of the above-mentioned polypropylene resin and the modified polyolefin resin in an arbitrary ratio may be used.
  • polystyrene-based resin examples include polypropylene, polyethylene, and ethylene-propylene copolymer, and the resin is not particularly limited as long as it contains an olefin as a monomer.
  • the ⁇ , ⁇ -unsaturated carboxylic acid or its derivative used as a modifier for polyolefin resins includes unsaturated carboxylic acids such as maleic acid, fumaric acid, itaconic acid, acrylic acid, tetrahydrophthalic acid, citraconic acid, crotonic acid, and isocrotonic acid.
  • Carboxylic acids and the like can be mentioned, and examples thereof include anhydrides, acid halides, amides, imides, esters and the like. Specific examples thereof include maleic anhydride, monomethyl maleate, dimethyl maleate, maleimide, and glycidyl maleate. Of these, anhydrides are preferred, and maleic anhydride is particularly preferred.
  • radical generator examples include organic or inorganic peroxides, and examples thereof include t-butyl peroxybenzoate, t-butyl hydroperoxide, methyl ethyl ketone peroxide, potassium peroxide, and hydrogen peroxide.
  • the number average molecular weight (Mn) of the polyolefin modified with the unsaturated carboxylic acid is preferably 20,000 to 100,000, more preferably 25,000 to 95,000, and 30, It is more preferably 000 to 95,000.
  • the number average molecular weight (Mn) can be measured by gel permeation chromatography (GPC, mobile phase: chloroform, standard substance: polystyrene).
  • the resin composition when the component (d) (inorganic filler) and the component (a) (polyphenylene ether-based resin) are easily adhered to each other, the resin composition exhibits excellent impact resistance and vibration fatigue characteristics.
  • the surface of the inorganic filler has low adhesive strength with the resin and other substances, and even when the inorganic filler is uniformly mixed with the resin, the interface strength between the inorganic filler and the resin is extremely low, and the inorganic filler The effect of improving the strength of the composition by the addition may not be sufficiently obtained. In order to enhance the effect of this strength improvement, it is desirable to bond the resin and the inorganic filler by a chemical bond.
  • the surface of the inorganic filler has extremely low chemical reactivity, it may be difficult to cause such a chemical reaction with the inorganic filler as it is. Therefore, while surface-treating the inorganic filler, (f) a polyolefin modified with an unsaturated carboxylic acid is used in combination. As a result, the surface of the inorganic filler via the component (f) can be chemically bonded to the resin, and the component (d) (inorganic filler) and the component (a) (polyphenylene ether-based resin) can be easily adhered to each other. , The resin composition will exhibit excellent impact resistance and vibration fatigue characteristics.
  • the inorganic filler and the surface treatment agent are easily decomposed in the presence of water, which may lead to a decrease in strength.
  • the above-mentioned hydrotalcite-like compound is added or the component (d) containing a compound containing an acid functional group is used in the surface treatment agent, decomposition and deterioration of physical properties in the presence of water can be suppressed, which is excellent. It is possible to obtain impact resistance and vibration fatigue characteristics.
  • the component (d) (inorganic filler) is preferably glass fiber from the viewpoint of strength and cost.
  • the glass fiber is subjected to a silane coupling treatment in which a silane compound is reacted with the Si—OH group existing on the surface of the glass fiber, so that the surface of the glass fiber and the resin via the component (f) are bonded to each other. Chemical bonding is possible.
  • a silane coupling treatment in which a silane compound is reacted with the Si—OH group existing on the surface of the glass fiber, so that the surface of the glass fiber and the resin via the component (f) are bonded to each other. Chemical bonding is possible.
  • a hydrotalcite-like compound or the component (d) containing a compound containing an acid functional group in the surface treatment agent.
  • the content of the component (f) in the present embodiment is 0.1% by mass or more from the viewpoint of impact resistance and vibration fatigue characteristics of the resin composition when the resin composition of the present embodiment is 100% by mass. It is preferably 0.2% by mass or more, more preferably 0.5% by mass or more, and more preferably 20% by mass or less, preferably 15% by mass or less, and 10% by mass. The following is more preferable.
  • the resin composition may contain a phosphorus compound.
  • the phosphorus compound include an organic phosphorus compound, red phosphorus, an inorganic phosphate and the like.
  • the organic phosphorus compound is not particularly limited as long as it is a phosphorus compound having an organic substituent (in the present embodiment, including a phosphorus compound having a PC bond and a POC bond), but is not limited to a phosphoric acid. Examples thereof include esters (hereinafter, also referred to as “phosphates”), phosphite esters (hereinafter, also referred to as “phosphates”), and phosphonite.
  • phosphates trimethyl phosphate, triethyl phosphate, tripropyl phosphate, tributyl phosphate, tripentyl phosphate, trihexyl phosphate, tricyclohexyl phosphate, triphenyl phosphate, and trickre, which are used as flame retardants.
  • Phosphate compounds such as dizyl phosphate, trixylenyl phosphate, cresil diphenyl phosphate, dicredyl phenyl phosphate, dimethyl ethyl phosphate, methyl dibutyl phosphate, ethyl dipropyl phosphate, hydroxyphenyl diphenyl phosphate; these were modified with various substituents.
  • Modified phosphate ester compounds examples include various condensation types of condensed phosphate ester compounds.
  • phosphites trisnonylphenyl phosphite, triphenylphosphite, tris (2,4-di-t-butylphenyl) phosphite, bis (2,4), which are also used as phosphorus-based antioxidants.
  • Examples of phosphonite include tetrakis (2,4-di-tert-butylphenyl) 4,4'-biphenylenediphosphonite and tetrakis (2,4-di-tert-butyl-5 methylphenyl) 4,4'.
  • -Biphenyl range phosphite and the like.
  • the phosphorus element contained in the resin composition is preferably 0.3% by mass or less, preferably 0.3% by mass or less, when the resin composition is 100% by mass, from the viewpoint of water resistance and vibration fatigue characteristics. It is more preferably 2% by mass or less, and particularly preferably 0.1% by mass or less.
  • a method for measuring the phosphorus element content in the resin composition for example, 0.25 g of a thermoplastic resin composition that has been previously dried is precisely weighed in a fluororesin container in a clean room, and sulfuric acid and nitric acid are used therein. Is added and pressurized acid decomposition is performed with a microwave decomposition apparatus to obtain a decomposition solution.
  • a method of measuring by an absolute calibration curve method using an ICP mass spectrometer (cobalt as an internal standard) for a measurement solution obtained by weighing 25 mL of this decomposition solution to obtain a measurement solution can be mentioned. More specifically, it can be measured by the method described in Examples described later.
  • the method for coloring the resin composition is not particularly limited, and one or more colorants selected from known organic dye pigments and inorganic pigments can be used.
  • organic dyeing pigment examples include azo pigments such as azo lake pigments, benzimidazolone pigments, diarilide pigments and condensed azo pigments, phthalocyanine pigments such as phthalocyanine blue and phthalocyanine green, isoindolinone pigments, quinophthalone pigments and quinacridone pigments. , Perylene pigments, anthraquinone pigments, perinone pigments, condensed polycyclic pigments such as dioxazine violet, azine pigments, carbon black and the like.
  • the carbon black preferably has a dibutyl phthalate (DBP) absorption amount of less than 250 mL / 100 g, preferably less than 150 mL / 100 g, and a nitrogen adsorption specific surface area of less than 900 m2 / g, more preferably less than 400 m2 / g. ..
  • DBP dibutyl phthalate
  • the DBP absorption amount and the nitrogen adsorption specific surface area referred to here refer to values measured by the methods specified in ASTM D2414 and JIS K6217, respectively.
  • the acid dye include Solvent Black 5 (CI 50415, CAS No. 11099-03-9) and Solvent Black 7 (CI 50415: 1, CAS No. 8005-20-5) in the Color Index. / 101357-15-7), Acid Black 2 (CI 50420, CAS No. 8005-03-6 / 68510-98-5).
  • the inorganic pigment examples include metal oxides other than iron oxide such as titanium oxide, zinc oxide and chromium oxide, and composite metal oxides such as titanium yellow, cobalt blue and ultramarine blue.
  • the preferable amount of the colorant added is 2% by mass or less for carbon black, 2% by mass or less for azine dyes, and 8% by mass or less for inorganic pigments, assuming that the entire resin composition is 100% by mass. More preferable amounts are 1% by mass or less for carbon black, 1% by mass or less for azine dyes, and 5% by mass or less for inorganic pigments.
  • additive components include other thermoplastic resins such as polyesters and polyolefins, plasticizers (low molecular weight polyolefins, polyethylene glycols, fatty acid esters, etc.), antistatic agents, nucleating agents, fluidity improvers, reinforcing agents. , Various peroxides, spreading agents, copper-based heat stabilizers, organic heat stabilizers typified by hindered phenol-based oxidative deterioration inhibitors, antioxidants, ultraviolet absorbers, light stabilizers and the like.
  • the specific preferable addition amount of these components is 15% by mass or less, more preferably 13% by mass or less, still more preferably 10% by mass, respectively, when the total resin composition is 100% by mass. It is as follows.
  • the component phase (b) is a matrix phase and the component phase (a) is a dispersion phase. It is more preferable that the b) component phase is a matrix phase and the (a) component phase is a dispersed phase.
  • the component phase (a) contains the component (a), and may be composed of, for example, a component containing the component (a) and the component (c), or the component (a) and the component (c). It may be composed of a component containing and (d) component, or may be composed of (a) component.
  • the component phase (b) contains the component (b) and may be composed of a component containing the component (b) and the component (d), or the component (b), the component (d) and ( It may be composed of a component including e) a component, or may be composed of a component (b).
  • the morphology of the resin composition can be observed with a transmission electron microscope (TEM) or the like.
  • the component phase (a) is preferably dispersed with an average minor axis diameter of 2 ⁇ m or less. Further, it is more preferable that the average minor axis diameter of the component phase (a) is dispersed at 10 nm or more and 1 ⁇ m or less from the viewpoint of impact resistance. Further, it is preferable that the average major axis diameter / average minor axis diameter is dispersed in 1 to 10.
  • the average minor axis diameter and the average major axis diameter can be determined by observation with a transmission electron microscope (TEM) or the like.
  • the component (c) is not only included in the component phase (a), but is also included in the component phase (a) by taking a morphology in which the component phase (a) is surrounded by the component (c). )
  • the component can take a more stable dispersed state thermally, which is preferable from the viewpoint of impact resistance.
  • the phase containing the linear component (c) having a length of 75 nm or more is contained inside the phase containing the component (a). It is preferable to disperse in this state from the viewpoint of impact resistance. The reason why the impact resistance is improved by such a dispersed state is not clear, but the morphology in which the component phase (a) having relatively inferior impact resistance contains the component (c) having excellent impact resistance. Therefore, it is presumed that the impact resistance of the resin composition is improved.
  • the phase containing the linear component (c) having a length of 75 nm or more contained inside the phase containing the component (a) is ruthenium tetroxide, and the component (b) and the component (c) are used.
  • the stained and observed TEM image it is a linear phase that is stained relatively blacker than the component (a), is present in the phase containing the component (a), and further, its presence is ( It means a phase other than the interface between the phase containing a) component and the phase containing (b) component.
  • those containing the component (b) in the dispersed phase may be dyed relatively blacker than the component (a) because the dispersed phases are fused with each other. It is excluded from the "phase containing the linear component (c) having a length of 75 nm or more contained inside the phase containing the component (a)".
  • phase containing the component (c) is (a). Even if it is connected to the phase containing the component (c) existing at the interface between the phase containing the component () and the phase containing the component (b), the component (c) contained in the phase containing the component (a) is contained. Phase.
  • the phase containing the component (c) existing at the interface between the phase containing the component (a) and the phase containing the component (b) is excluded.
  • the length of the phase containing the component (c) extending away from the interface is defined as the length of the phase containing the component (c) contained in the phase containing the component (a).
  • the phase containing the linear component (c) may be formed by bending or branching, may draw an arc, may be bifurcated or more, or may be repeatedly connected. In this case, the total length of the phase containing the component (c) extending away from the interface in the phase containing the component (a) was included in the phase containing the component (a) (c). ) The length of the phase containing the component.
  • FIG. 1 shows a state in which 10 or more of the phases containing the component (a) include a phase containing a linear component (c) having a length of 75 nm or more. Note that FIG. 1 is an image of the resin composition of Example 2 described later.
  • the phase containing the linear component (c) contained inside the phase containing the component (a) is stained with ruthenium tetroxide to stain the components (b) and (c) to obtain a TEM. It is an image observed using.
  • the portion dyed in light gray is the phase containing the component (a)
  • the lightest part is the phase containing the component (b)
  • the portion dyed in dark gray or black is (c). )
  • the length of the phase containing the linear component (c) is preferably 75 nm or more from the viewpoint of impact resistance.
  • the width of the phase containing the linear component (c) contained inside the phase containing the component (a) is preferably 1 to 1000 nm, more preferably, from the viewpoint of obtaining more excellent vibration fatigue characteristics. Is 1 to 500 nm.
  • the above numerical value is an average value obtained by observing the linear (c) component present in any 100 (a) dispersed component phases in an image obtained by observing an arbitrary cross section of the resin composition by TEM.
  • Examples of the method for controlling the morphology as described above include (c) a method for adjusting the vinyl content of the component, the structure of each block portion, and a molecular weight, (a) a method for appropriately adjusting the molecular weight of the component, and polypropylene ether.
  • Examples thereof include a method of adjusting the blending ratio of the based resin (a) and the polypropylene-based resin (b), and a method of dividing the polypropylene-based resin (b) from a plurality of raw material supply ports and supplying the polypropylene-based resin (b) to an extruder.
  • it is most effective to adjust the vinyl content and molecular weight of the component (c).
  • the morphology tends to be suitable, but if it is too high, it may be necessary to adjust the addition amount. .. If the ratio of the component (a) to the total of the polyphenylene ether resin (a) and the polypropylene resin (b) is too large, the component (a) becomes a matrix, and the morphology tends to be unfavorable.
  • test pieces stained with ruthenium tetroxide (b) and component (c) were subjected to a transmission electron microscope (trade name "HT7700", manufactured by Hitachi High-Technologies Corporation). Is used to shoot at a shooting magnification of 10,000 times and an acceleration voltage of 100.0 kV. From the acquired observation image, the visual field is selected so that (a) 100 or more component phases (dispersed phases) are contained.
  • the obtained morphology image (printing paper) was captured using a scanner (device: RIKOH MPC5503, condition: full-color photographic paper photograph, resolution 300 dpi) and digitized.
  • the image analysis software uses Image Pro10 to perform binarization processing (white / black) on the digitized image under the Auto conditions installed in Image Pro10.
  • the admixture (c) is relatively black compared to (a) the polyphenylene ether resin and (b) the polypropylene resin, which are relatively white to gray, and thus can be distinguished.
  • phase (dispersed phases) containing the component (a) are arbitrarily selected, and the average major axis diameter and the average minor axis diameter of the phase containing the component (a) are measured.
  • the length and width of the phase containing the component (c) contained inside the phase containing the component (a) are measured.
  • defects that occur in the measured cross section may be reflected in the morphology image, but the image range to be binarized is that. It shall be selected so as not to include such a part.
  • the melt mass flow rate of the resin composition of the present embodiment is preferably 1 to 20 g / 10 min, more preferably 2 to 20 g / 10 min, and further preferably 3 to 20 g / 10 min.
  • the melt mass flow rate refers to a value measured at 250 ° C. and a load of 10.0 kg according to ISO1133.
  • the resin composition of the present embodiment can be produced by melt-kneading the above-mentioned components (a) to (e), and if necessary, the component (f) and other components.
  • the method for producing the resin composition of the present embodiment is not particularly limited as long as the components (a) to (e), and if necessary, the component (f) and other components can be melt-kneaded.
  • a suitable method for producing the resin composition of the present embodiment is a step of melt-kneading the entire amount of the component (a) and all or part of the component (b) and the component (c) to obtain a kneaded product (1).
  • the step (1-3) of adding the entire amount of the component (d) to the kneaded product obtained in the step (1-2) and further melt-kneading is included.
  • the step of adding the component (e) may be any one of step (1-1), step (1-2), and step (1-3), and may be added alone or dividedly. Good. The same applies to the component (f).
  • a suitable method for producing the resin composition of the present embodiment may be a method of melt-kneading in multiple stages.
  • the multi-stage is not particularly limited as long as it has two or more stages.
  • Such a method in the present embodiment is described in, for example, In the first step, the whole amount of the component (a), a part of the component (b), the whole amount of the component (c), and the whole amount of the component (e) are melt-kneaded to obtain pellets. In the second step, the pellets obtained in the first step, the balance of the component (b), the component (d), and if necessary, the component (f) are added, and further melt-kneaded. including. In this case, the entire amount of the component (b) may be added in the second step.
  • a resin composition (masterbatch) containing a specific component at a high concentration is prepared in advance, and then the masterbatch is diluted to obtain each component.
  • masterbatch method for obtaining a resin composition containing the above in a desired concentration is also a masterbatch method for obtaining a resin composition containing the above in a desired concentration.
  • Such a method in the present embodiment is described in, for example,
  • the total amount of the component (a), a part of the component (b), the total amount of the component (c), and the total amount of the component (d) are melt-kneaded, and the component (d) is obtained from the concentration in the final composition.
  • the process of obtaining masterbatch pellets containing a high concentration of In the second step, the masterbatch pellet, the remainder of the component (b), and if necessary, the component (f) are added, and further melt-kneaded to obtain the final composition. including. In this case, the entire amount of the component (b) may be added in the second step.
  • the melt kneader preferably used for melt-kneading each component in the above-mentioned manufacturing method is not particularly limited, and is, for example, a multi-screw extruder such as a single-screw extruder or a twin-screw extruder.
  • a multi-screw extruder such as a single-screw extruder or a twin-screw extruder.
  • examples thereof include a heat-melt kneader using an extruder, a roll, a kneader, a lavender plastograph, a Banbury mixer and the like, and a twin-screw extruder is particularly preferable from the viewpoint of kneadability.
  • Specific examples of the twin-screw extruder include the ZSK series manufactured by Coperion, the TEM series manufactured by Toshiba Machine Co., Ltd., and the TEX series manufactured by Japan Steel Works, Ltd.
  • the type and standard of the extruder are not particularly limited and may be known.
  • the L / D (barrel effective length / barrel inner diameter) of the extruder is preferably 20 or more, more preferably 30 or more, more preferably 75 or less, and further preferably 60 or less. preferable.
  • the structure of the extruder may be provided with two or more different raw material supply ports, two or more vacuum vents, and one or more liquid addition pumps (described later), and the raw materials regarding the arrangement of these facilities. From the first raw material supply port on the upstream side, the first vacuum vent downstream from the first raw material supply port, the second raw material supply port downstream from the first vacuum vent, and the second raw material supply port. It is more preferable to have a liquid addition pump downstream and a second vacuum vent downstream of the liquid addition pump from the viewpoint of impact resistance.
  • the method of supplying the raw material at the second raw material supply port is not particularly limited, and the method of simply adding from the upper open port of the raw material supply port is also a method of adding from the side open port using a forced side feeder.
  • a method of adding from the side opening using a forced side feeder is preferable.
  • the melt-kneading temperature may be usually 270 to 320 ° C.
  • the temperature between the first raw material supply port and the second raw material supply port is 300 ° C. or higher and 320 ° C. or lower.
  • the set temperature is set between the first raw material supply port and the second raw material supply port and the portion downstream from the second raw material supply port.
  • the set temperature between the first raw material supply port and the second raw material supply port is set to 300 ° C. or higher and 320 ° C. or lower, and the portion downstream from the second raw material supply port is set.
  • the temperature is preferably 270 ° C. or higher and lower than 300 ° C.
  • the screw rotation speed is not particularly limited and may be usually 100 to 1200 rpm.
  • the molded product of the present embodiment comprises the resin composition of the present embodiment described above.
  • the molded body of the resin composition of the present embodiment is not particularly limited, and examples thereof include automobile parts, interior / exterior parts of electric devices, and other parts.
  • the automobile parts are not particularly limited, and are, for example, exterior parts such as bumpers, fenders, door panels, various moldings, emblems, engine hoods, wheel caps, roofs, spoilers, and various aero parts; instrument panels, consoles, etc.
  • Interior parts such as boxes and trims; secondary battery battery parts mounted on automobiles, electric vehicles, hybrid electric vehicles and the like; lithium ion secondary battery parts and the like.
  • the interior / exterior parts of electrical equipment are not particularly limited, and are, for example, various computers and their peripherals, other OA equipment, cabinets such as televisions, videos, and various disc players, chassis, refrigerators, air conditioners, and liquid crystals. Examples include parts used in projectors. Other parts include electric wires / cables obtained by coating metal conductors or optical fibers, fuel cases for solid methanol batteries, fuel cell water distribution pipes, water cooling tanks, boiler exterior cases, ink peripheral parts / members for inkjet printers. , Furniture (chairs, etc.), chassis, water pipes, joints, etc.
  • the molded product of the present embodiment can be produced by molding the resin composition of the present embodiment described above.
  • the method for producing the molded product of the present embodiment is not particularly limited, and examples thereof include injection molding, extrusion molding, extrusion malformed molding, hollow molding, compression molding, and the like, and the effects of the present embodiment are more effective. Injection molding is preferable from the viewpoint of obtaining the above.
  • A Polyphenylene ether resin
  • a-1 Polyphenylene ether resin obtained by oxidative polymerization of 2,6-xylenol
  • the reduced viscosity (0.5 g / dL, chloroform solution, measured at 30 ° C.) of the polyphenylene ether resin is , 0.52 dL / g.
  • A-2) Polyphenylene ether resin obtained by oxidative polymerization of 2,6-xylenol
  • the reduced viscosity (0.5 g / dL, chloroform solution, measured at 30 ° C.) of the polyphenylene ether resin is 0.40 dL / g. there were.
  • Admixture (c-1) A block copolymer having a block structure of II-I-II-I was synthesized by using a known method as a polymer block I made of polystyrene and a polymer block II made of polybutadiene. Hydrogenation was performed on the synthesized block copolymer by a known method. No modification of the polymer was performed. The physical properties of the obtained unmodified hydrogenated block copolymer are shown below.
  • a block copolymer having a block structure of II-I-I-I was synthesized by using a known method as a polymer block I made of polystyrene and a polymer block II made of polybutadiene.
  • Inorganic filler (d-1) A glass fiber having an average fiber diameter of 13 ⁇ m surface-treated with a surface treatment agent containing an acid functional group. It was confirmed by measurement by Py-GC / MS that the surface treatment agent contained an acid functional group.
  • a twin-screw extruder (ZSK-25, manufactured by Coperion) was used as a melt-kneader used for producing the resin compositions of each example and each comparative example.
  • the L / D of the extruder was 35.
  • a first raw material supply port was provided on the upstream side with respect to the flow direction of the raw material, a second raw material supply port was provided downstream of the first raw material supply port, and a vacuum vent was provided further downstream. Further, as a method of supplying raw materials to the second supply port, a side feeder is used to supply the raw material from the side opening port of the extruder.
  • the resin pellets obtained above are used and supplied to a small injection molding machine (trade name: IS-100GN, manufactured by Toshiba Machine Co., Ltd.) set at 240 to 280 ° C. under the condition of a mold temperature of 60 ° C., which will be described later.
  • Evaluation test pieces for each test were prepared.
  • a JIS K7139 type A1 test piece was prepared and allowed to stand in an environment of 80 ° C. for 24 hours using a gear oven to perform heat history processing. This test piece was used as a test piece for measuring impact resistance and water resistance and a test piece for morphology observation.
  • a No. III type test piece conforming to the cantilever bending test method of JIS-7119 was prepared for the special evaluation of vibration fatigue.
  • the average minor axis diameter of the phase containing the component (a) was determined from the observation image by the above-mentioned method. Those having an average minor axis diameter of 10 nm or more and 1 ⁇ m or less were designated as “ ⁇ ”, and those not having an average minor axis diameter were marked with “x”.
  • a polypropylene / polyphenylene ether resin composition having excellent water resistance can be obtained even when an inorganic filler is added.

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US3257357A (en) 1963-04-01 1966-06-21 Du Pont Copolymers of polyphenylene ethers
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